Copper compounds of primary resorcinol trisazo-dyestuffs and their manufacture



Patented Dec. 19, 1939 PATENT OFFICE "COPPER COMPOUNDS OFPRIMARY RE-SORGINOL TRISAZO DYESTUFFS AND THEIR MANUFACTURE ,I' ritz 'DObler andHans'Buess, Basel, Switzerland, assignors to'the firm J. R. Geigy S. A.,Basel,

' Switzerland cult was found that new and useful-copper compounds :ofprimary ortho-hydroxy-resorcinol trisazo-dyestufis are obtained-ifresorcinol is coupledin an alkaline solution in the first place with .5adiazo-compound derived fromaznegatively substituted ortho-aminophenol,secondly with any desired diazo-compound and finally with a diazotized.aminodiphenylamine sulphonic acid and treated with a copper salt. Thenew dyestuff- 10 metal compounds distinguish themselves by theirvaluable clear'and neutral-brown tints and as already known fortrisazo-dyestuffs of analogous constitution they havea very goodafllnity for weighted and unweighted silk and leather tanned 15 withvegetable} and chrome-tanning agents, but

practically not for wool.-

, "Brown trisazo-dyestufis lof-resorcinol are 3,1? ready known by the.GermanvPatent 629,743. According to .its processgresorcinol is coupledin any so succession in an alkalinemedium with 1 molecule of idia'zotized I4-aminodiphenylamine-2-sulphonic acid. and 1,molecule ofdiazotized 2-amino-1-hydroxy-6-nitrobenzene-I4-sulphonic acid or,diazotized 2 amino 9.]. hydroXy-4:G-dinitrobenzene,

A35 with l/ molecule of each of the two diazo-components respectively,and finally with 1 molecule of a diazo-compound ofrthe benzeneserieswhich may be nitrated or halogenated. In the example which iscustomarily regarded as the best modus :30 of performance 1 of theprocess, diazotized 4- aminodiphenylamine-2 sulphonic acid is mentionedas the first diazo component. In accordance with the practical-'knowledge gained from these and similar primary trisazo dyestufis the 35coupling. succession is said to, be. without influ- -45 component. Thefirst one must be'a negatively substituted ortho-aminophenol the lastone a diazotized aminodiphenylamine' sulphonic acid; the second diazo-component being any desired one. In the first" place areusedadvantageously as o ponent derived from a negatively substitutedortho-aminophenol for example 4- or -nitro-2-aminopheno1, .the3-amino-2-hydroxy- .benzoic acid, the Z-nitro-(i-aminol-hydroxybenzenel-sulphonic acid, the isomeric 4:6;1;2-c

No Drawing. Application June 29, 1937, Serial No. 151,064. InSwitzerland July 13, 1936 18 Claims. (01. 260- 145)2-amino-1-hydroxybenzene-4-sulpho-6-carboxylic acid,4-chloro-2-amino-1-hydroxybenzene-6- sulphonic acid; in the third placeaminodiphenyl amine sulphonic acids with good coupling capacity'haveshown to be of great advantage, for example the4-nitro-4'-aminodiphenylamine2 sulphonic acid, the isomeric2z4z4-compound, 4-.

' o-chloro-p-nitraniline, 4-nitraniline-2-sulphonic acid or theisomeric2:4-compound, nitroamino diphenylamine sulphonic acids as indicatedabove are used to great advantage.

Instead of the single diazo compounds indicated in the three groupsabove, also mixtures of different diam-components from the same groupsmay be used together;

The new dyestuffs distinguish themselves from those of German Patent No.629,743 by their much clearer, neutral brown shades, due to the smoothcourse of their production. According to the process of the abovementioned patent the couplings of which are foaming strongly, ugly dullbrown tones are obtained which,juclging by their tint, cannot betrisazo-dyestufis, or only very impure primary ones. Moreover, thefastness properties of the metal compounds of the new dyestuffs aresuperior to those of the dyearninodiphenylamine-Zsulphonic acid and 4'-stuffs made according to the known process.

This refers especially to the fastness to light, partly also to thebetter fast'ness to fat liquor of the leather dyeings and the betterfastness to washing and water of the dyeings on weighted and unweightedsilk. If the dyestuffs of German Patent 629,743 are converted into themetal compounds, especially into the copper compounds, tints from brownwith violet shade to distinctly violet in shade are obtained which areof little interest.

For the after-treatment of the dyestufis the water soluble compounds ofcopper may be mentioned, such as copper sulphate, copper chloride,copper acetate and so on. The'treatment with the metal-salts may be madein substance, in the dyeing bath, by after treatment of the dyeings oraccording to any other known process. The application of coppercompounds proves to be ofv great advantage, the decomposition therewithgoing on very rapidly and smoothly.

The following examples illustrate the invention, the parts being byWeight:

Example 1 23.4 parts of 2-nitro-6-amino-l-hydroxybenzenel-sulphonic acidare dissolved in 150 parts of water of 80 C. with 6 parts of anhydroussodium carbonate, cooled down to 5 C., acidified with parts ofhydrochloric acid (30%) and diazotized with 6.9 parts of nitrite.Temperature 2 C. The diazonium compound is added during 10 minutes to asolution of 11 parts of resorcinol and parts of caustic soda lye (30%)in water and ice at 0 C. After 1 hour a solution of 13.8 parts ofdiazotized 4-nitro-1- aminobenzene is allowed to run into the solutionof the monoazodyestuff, temperature 0 C., 24 parts of anhydrous sodiumcarbonate are added and a solution of 30.9 parts of 4-nitro-4'-aminodiphenylamine-2-sulphonic acid made in usual manner is allowed toflow induring minutes approximately. After stirring for several hoursthe dyestufi is separated out with 75 parts of hydrochloric acid (30%)and 300 parts of salt and filtered.

If in the place of the Z-nitro-S-amino-l-hydroxybenzene--sulphonic acidas first component the isomeric 4:621:2-compound or picramic acid, inthe second place a halogenated nitraniline such as2-chloro-4-nitraniline, a nitraniline-sulphonic acid such as theal-nitraniline-Z- sulphonic acid or the isomeric 2:4-compound or the4-nitro-4-aminodiphenylamine-2-sulphonic acid or1-naphthylamine-5-sulphonic acid, sulphanilic acid and so on are used,brown trisazodyestufis with similar properties are obtained.

For the production of the metal compound the filter-cake obtained asdescribed above is dissolved in 2400 parts of water, 52 parts ofcrystallized copper sulphate are added, heated up to -95 C. and kept for30 minutes. When the reaction is complete there is allowed to cool downto 50 C. and then the coppered dyestufi precipitated with 400 parts ofsalt, filtered and dried at 80 C.

In the place of copper sulphate there may be used any other salt beingsoluble in acid medium; for example also copper carbonate may be used.

Example 2 23.3 parts of3-amino-2-hydroXybenzene-1-carboxylic-S-sulphonic acid are dissolved inparts of water of 80 C. with the aid of 12 parts of anhydrous sodiumcarbonate, cooled down to 0 C., precipitated with 34 parts ofhydrochloric acid (30%) and diazotized with a solution of 6.9 parts ofsodium nitrite. Meanwhile 11 parts of resorcinol are dissolved in 30parts of water, 20 parts of anhydrous sodium carbonate are added at 0 C.and then the diam-compound of 3- amino 2 hydroxybenzene 1-carboxylic-5-su1 phonic acid. The coupling being complete, the solutionof the monoazo-dyestuff is again cooled to 0 C., 20 parts of anhydroussodium carbonate and 20 parts of caustic soda lye (30%) are added and21.8 parts of 4-nitro-l-aminobenzene-Z- sulphonic acid, diazotized inthe usual manner, are allowed to flow in at 0 C. When coupling iscomplete, 20 parts of anhydrous sodium carbonate and 6.0 parts ofcaustic soda lye are given into the solution of the disazo-dyestufi andcoupled at 0 C. with the diazo-compound made in the usual manner from30.9 parts of 4-nitro- 4-aminodiphenylamine-2-sulphonic acid. Thecoupling being finished, the trisazo-dyestufi is precipitated with 400parts of salt, 100 parts of potassium chloride and parts of hydrochloricacid (30%) and filtered.

For the production of the metal compound the filtered cakes aredissolved in 2000 parts of water, 52 parts of crystallized coppersulphate and 28 parts of sodium acetate or equivalent parts of formateare added and heated at 9095 C. for 30 minutes. The dyestuff containingcopper is precipitated with 400 parts of salt, filtered and dried at 80C.

It dyes silk and leather beautiful brown shades of excellent fastness tolight and other good fastness properties.

In the second place the diam-compound of nitraniline or in the secondand third place the amines mentioned in Example 1 for the same couplingrange may be used. The dyestuffs obtained have similar properties.

The conditions for coupling in the above examples may be varied forexample by pre-addition in parts of the caustic or carbonate alkali oronly by adding them after the dyestufi-forming component having beenjoined together. In just the same manner other .alkalies, such asammonia may be used.

What we claim is:

1. A process for the production of copper compounds of primaryresorcinol trisazo-dyestufis, consisting in reacting a water solublecopper .salt with a trisazo-dyestuif of the general formula wherein R1means the radical of the first -coupled diazo-compound made from anegatively substituted orthoaminophenol, R2 means the radical of thesecondly coupled diazo-compound made from any desired aromatic amine and.R: means the radical of the finally coupled diazocompound made from anaminodiphenylamine sulphonic acid, the trisazo-dyestuff being made inthis order of coupling in alkaline solution.

2. A process for the production of copper compounds -of primaryresorcinol trisazo-dyestuffs, consisting in reacting a water solublecopper salt with a trisazo-dyestufi of the general formula wherein R1means the radical of the first coupled diazo-compound made from anegatively substituted orthoaminophenol, R2 means the radical of thesecondly coupled diazo-compound made from a nitroamine of the benzeneseries and Rs means the radical or the finally coupled diazocompoundmade from an aminodiphenylamine sulphonic acid, the trisazo-dyestuffbeing made in this order of coupling in alkaline solution.

3. A process 'for the production of copper'compounds of primaryresorcinol trisazo-dyestuifs, consisting in reacting a water solublecopper salt 'With a trisazo-dyestuff of the general formula wherein R1means the radical of the first coupled diazo-compound made from anegatively substituted ortho-aminophenol, selected from the Ill groupconsisting: of 4-nitro-2-1aminopheno1,l 5- nitro-'2-aminophenol,-3-amino-2-hydroxybenzoic' acid, 4-chloro-2-amino-l-hydroxybenzene-fi sulphonic acid, Z-nitro-G-amino- 1-hydr'oxybenzene- 4-sulphonicacid,4'-nitro'6-a'mino-1-hydroxybenzene-'2-sulphonic acid, 45(i-dinitr0-2-aminol-hy'droxybenz'ene, 2-amino- 1 hydroxybenzene-4-sulpho-6-carboxylic acid, Rzmeans the radical of the secondlycoupleddiazo-compoundmade from a nitroamine, of the benzene series,selected from thegroup consisting of' ortho-, meta'-, para-nitraniline,ortho chloro-para nitraniline,

4-nitraniline-2-sulphonic acid, 2-nitraniline 4 sulphonic acid, and theaminodiphenylamine sulphonic acids mentioned in this claim under BaandR3 means the radical of the finally coupled diazo-compound made 5 froman aminodiphenylamine sulphonic acid, selected from'the group consistingof 4-nitro 4' aminodiphenylamine-2-sulphonic acid,2-nitro-4'-aminodiphenylamine-4-sulphonic acid,.4"-methoxyi-aminodiphenylamine-Z-sulphonic acidand,i-aminodiph'enylamine-2-sulphonic acid, the trisazodyestuff being madeinthis order of coupling in alkaline solution.

4. A process forthe production of copper compounds of primary resorcinoltrisazo-dyestuffs, consisting in reacting copper sulphate with ahisazo-dyestuff of the general formula wherein Rimeans'the radical ofthe'first coupled diazo-compound made from a negatively substitulted'orthoaminop-henol, R2 means the radical of thesecondly coupleddiazo-compound made from any desired aromatic amine-and R3meanstheradical of the finally coupled diazo compound made from anaminodiphenylamine sulphonic acid, the trisazo-dyestufi being made inthis order of coupling in alkaline solution.

5. A process for the production of copper compounds of primaryresorcinol trisazo-dyestuffs, consisting in reacting copper sulphatewith a'trisazo-dyestuff of the general formula wherein R1 means theradical of the first coupleddiazo-compound made from a negativelysubstituted orthoaminopheno-l, R2 means the I radical of the secondlycoupled diazo-compound made from a nitroamine of the benzene series andR3 means the radical of the finally coupled diazo-compound made from anaminodiphenylamine sulphonic acid, the trisazo-dyestufi' being made inthis order of'coupling in alkaline solution. a I" 6. A process for theproduction of copper compounds of primary resorcinol trisazo-dyestufi's,consisting in reacting copper sulphate with a trisazo-dyestuff of thegeneral formula wherein R1 means the radical of the first cousulphonicacids mentioned in this claim under 7 R3, and. R3 means the radical ofthe finally coupled diazo-compound made from an aminodiphenylaminesulphonic acid, selected from the groupconsisting of 4-nitro 4'aminodiphenylamine-2 -'sulphonic acid, 2 nitro 4'aminodiphenylamine-4-sulphoni'c acid, 4' methoxy 4- aminodiphenylamine 2sulphonic acid and aminodipheny1amine-2-sulphonic .acid, thetrisazo-dyestuff being made in this order of coupling in alkalinesolution. r

7. A process for the production of the copper compound of a primaryresorcinol trisazo-dyestufi, consisting in reactinga copper saltselected 13 from the group of copper sulphate,,copper chloride, copperacetate and copperfo'rmate with atrisazo-dyestufl of thegeneral'fo-rmula the numbers 1, 2, 3 indicating the order of coupling inalkaline solution. l

8. A process for the'production of the copper compound of a primaryresorcinol trisazo-dyestuff, consisting in reacting a copper saltselected from the group of copper sulphate, copper chlof ride, copperacetate and copper formatewitha trisazo-dyestufi of the general formulaOnN the'numbers 1, 2, 3 indicating the order of" con pling in alkalinesolution.

3 9. A process for the production of the copper compound of a primaryresorcinol trisazo dyestuff, consisting in reacting a copper saltselected trom the group of copper sulphate, copper chlo-' ride, copperacetate and copper formate with a trisa'zo-dyestufi" of the generalformula HO OH OaN the numbers 1, 2, 3 indicating the order of couplingin alkaline solution.

10. The copper compounds of primary resorcinol trisazo-dyestufis of theprobable general formula wherein R1 means the radical of the firstcoupled diazo-compound made from a negatively substitutedortho-aminophenol, R2 means the radical of the secondly coupleddiazo-compound made from any desired aromatic amine and R3 means theradical of the finallycoupled diazo-compound made from anaminodiphenylamine sulphonic acid, the trisazo-dyestuff being made inthis order of coupling in alkaline solution, being dark powders solublein water to brown solutions dyeing silk and leather pure beautiful brownshades of very good fastness to light.

11. The copper compounds of primary resorcinol trisazo-dyestufis of theprobable general formula wherein R1 means the radical of the firstcoupled diazo-compound made from a negatively sub stitutedortho-aminophenol, R2 means the radical of the secondly coupleddiazo-compound made from a nitroamine of the benzene series and Rs meansthe radical of the finally coupled diazocompound made from anamino-diphenylamine sulphonic acid, the trisazo-dyestufi being made inthis order of coupling in alkaline solution, being dark powders solublein water to brown solutions dyeing silk and leather pure beautiful brownshades of very good fastness to light.

12. The copper compounds of primary resorcinol trisazo-dyestufis of theprobable general formula wherein R1 means the radical of the firstcoupled diazo-compound made from a negatively substitutedortho-aminophenol, selected from the group consisting ofl-nitro-Z-aminophenol, 5- nitro-Z-aminophenol, 3-amino-2-hydroxybenzoicacid, 4-chloro-2-amino-l-hydroxybenzene-G-sulphonic acid,2-nitro-6-amino-l-hydroxybenzenell-sulphonic acid, 4-nitro-6-amino-1-hydroxybenzene-Z-sulphonic acid, 4:6-dinitro-2-aminol-hydroxybenzene,2-amino-1-hydroxybenzene- 4-sulpho-6-carboxylic acid, R2 means theradical of the secondly coupled diazo-compound made from a nitroamine ofthe benezene series, selected from the group consisting of ortho-,meta-, para-nitraniline, ortho-chloro-para-nitraniline,4-mtraniline-2-sulphonic acid, 2-nitraniline-4- sulphonic acid, and theaminodiphenylamine sulphonic acids mentioned in this claim under R3, andR2 means the radical of the finally coupled diazo-compound made from anaminodiphenylamine sulphonic acid, selected from the group consisting of4-nitrol-aminodiphenylamine-2-sulphonic acid,2-nitro-4'-aminodiphenylaminel-sulphonic acid, 4'-methoxy-4-aminocliphenylamine-2-sulphonic acid and 4-aminodiphenylamine-Z-sulphonic acid, the trisazo-dyestuff being made inthis order of coupling in alkaline solution, being dark powders solublein water to brown solutions dyeing silk and leather pure beautiful brownshades of very good fastness to light.

13. The copper compounds of primary resorcinol trisazo-dyestuffs of theprobable general formula the two Xs being substituents selected from thegroup consisting of H, Cl, N02, SOaH and COOH, at least one beingdifferent from H, Y being a substituent selected from the group of H andS03. and R being the radical of the finally coupled diazo-compound madefrom an aminodiphenylamine sulphonic acid, being dark powders soluble inWater to brown solutions dyeing silk and leather pure beautiful brownshades of very good fastness to light.

14. The copper compounds of primary resorcinol trisazo-dyestuffs of theprobable general formula copper X being a substituent selected from thegroup consisting of H, N02, COOH and SOaI-I, Y being a the numbersll, 2,3 indicating the order of cou- O pling in alkaline solution, the saidcompound 1'7. The copper compound of a primary resorcinoltrisazo-dyestuff of the general formula ing a dark powder soluble inwater to a brown solution dyeing silk and leather pure beautiful brownshadesof very good fastness to light.

' FRJ ITZv DOBLER.

HANS BUESS.

soar: I l v H v substituent selected from the group of H and S03, thenumbers 1, 2, 3, indicatingthe order ofcouand B being the radical of thefinally coupled pling in alkaline solution, the said compoundbediazo-compound made from an aminodiphenyling a dark powder soluble inwater to a brown amine sulphonic acid, being dark powders solusolutiondyeing silk and leathervpure beautiful ble in water to brown solutionsdyeingv silk and brown shades of very good fastness 'to light. leatherpure beautiful brown shades of very good 18. The copper compound ofapr'imaryresorfastness to light. cinol trisazo-dyestufi of the generalformula OaN v N=N- --N N01 copper SOaH w a 16. Thecopper compound of aprimary resorthe numbers 1, 2, 3 indicating the order of 'coucinoltrisazo-dyestuff of the general formula pling in alkaline solution, thesaid compound be- 011 I I o I HO OH I I OzN N=N1l- 3N=N v OCH:

0 s 0 H S 3H I a I I v 5

